A STUDY  OF  THE  PRODUCTS 
OBTAINED  BY  THE  USE  OF 
ALCOHOLIC  POTASH  ON 
VARIOUS  COALS 


BY 


GRAEME  LINDLEY  ATKINSON 


THESIS 


FOR  THE 


DEGREE  OF  BACHELOR  OF  SCIENCE 


IN 


CHEMICAL  ENGINEERING 


COLLEGE  OF  LIBERAL  ARTS  AND  SCIENCES 


UNIVERSITY  OF  ILLINOIS 


1922 


I 322 
At  54 


UNIVERSITY  OF  ILLINOIS 


May 3 


THIS  IS  TO  CERTIFY  THAT  THE  THESIS  PREPARED  UNDER  MY  SUPERVISION  BY 


. Gr  ae  me  _ Li  nils  v _A  tk  i n8.ori- 


ITLED  ^ Stuay  of  the  Products  ottaineci  by  the  use 


of  Alcoholic  Pots.8h  on  Various  Coals 


IS  APPROVED  BY  ME  AS  FULFILLING  THIS  PART  OF  THE  REQUIREMENTS  FOR  THE 
degree  of  Bachelor  of  Science  in  Chemical  Engineering 


Instructor  in  Charge 


Approved  AT 


ACTING  HEAD  OF  DEPARTMENT  OF  __CHMJ_STRY  . 


Digitized  by  the  Internet  Archive 
in  2016 


https://archive.org/details/studyofproductsoOOatki 


ACKNOWLEDGEMENT. 

The  author  wishes  to  express  his  sincere  thanks 
to  Dr.  T.  E.  Layng  for  his  valuable  help  and 
direction  given  throughout  this  investigation. 


• - 

.. 


TABLE  OF  CONTENTS 


I.  Introduction 1. 

II.  Nature  of  the  Problem. 1. 

III . History 1. 

IV.  Theorectical 4. 

V.  Purpose  of  Investigation....  6. 

VI.  Experimental 7. 

VII.  Discussion 11. 

VI I I.  Summary 16. 

IX.  Bibliography.... 17. 


1. 


INTRODUCTION 

Coal,  although  compounded  of  the  element*  carbon,  oxygen, 
nitrogen,  sulphur,  and  inorganic  salts  is  a very  complex  material 

about  which  very  little  is  known.  A great  dkl  of  researoh  and 
investigation  has  been  carried  on  in  order  to  learn  more  about 
the  substances  or  compounds  that  make  up  this  complex.  The  three 
most  successful  methods  of  attacking  the  problem  have  been  found 
to  be  (l)  Microscopic  examination,  (3)  Separation  by  means  of 
reagents  and  solvents,  (3)  Study  of  the  products  resulting  from 
carbonization.  In  recent  years  it  has  been  found  that  the  best 
reeults  are  obtained  by  combining  the  second  and  the  third  methods. 
For  the  carbonization  of  coal  is  the  important  question  of  today 
and  the  future,  and  with  this  fact  in  view  the  combined  solvent 
and  carbonization  work  with  coal  has  been  carried  out.  Because  of 
the  rapid  depletion  of  our  good  coking  coals,  methods  for  coking 
what  are  now  poor  or  non-coking  coals  must  be  obtained.  In  order 
to  do  this  the  action  of  the  different  constituents  of  good  cok- 
ing coals  must  be  understood. 

NATURE  OF  THE  PROBLEM 

The  nature  of  the  problem  wa3  a study  of  the  products  obtain- 
ed from  various  coals  with  the  use  of  alcoholic  potash  as  a reagent. 

HISTORY 

A brief  history  of  the  use  of  reagent  and  solvents  on  coal 

nay  helP  t0  a better  understanding  of  the  problems  and  factors 

in  this  investigation. 

It  is  very  difficult  to  distinguish  between  those  substances 


I 


2 


which  are  considered  pure  solvents,  and  those  which  attack  the 
original  substances  and  are  considered  as  reagents.  The  pure 
solvents  are  benzene,  chloroform,  ethyl  alcohol,  acetone,  phenol, 
xylene,  anddi -phenol  ether.  The  reagents  which  have  been  used  are 
sulphuric  acid,  nitric  acid,  caustic  alkalies,  bromine,  ozone  and 
oxygen. 

The  first  work  by  solvents  was  done  by  Dr.  Stay the  1 on  coal 
in  1851.  He  extracted  a brown  coal  with  benzene,  chloroform, 
alcohol,  ethyl  ether,  acetone  and  petroleum  ether.  The  benzene 
extract  was  3 percent,  the  chloroform  extract  1.8  percent,  the 
alcohol  extract  2.4  percent. 

Reisnch  in  1885  ~ considered  coal  to  be  composed  of  two 
types  of  substances,  which  could  be  distinguished  by  their  action 
towards  alkaline  solutions.  With  an  alkaline  solution  he  was  able 
to  isolate  substances  which  were  very  characteristic  in  not  being 
attack  by  mineral  acids. 

Anderson  and  Roberta  in  1888  3 used  caustic  alkali  as  a 
reagent  for  coal.  They  found  that  boiling  weak  coking  coals  for 
one  and  one-half  hours  in  5 percent  alkali  destroyed  their  coking 
properties,  while  it  had  no  effect  upon  strong  coking  coals.  This 
indicated  that  only  some  of  the  resinic  constituents  were  saponif- 
iable. They  heated  a large  number  of  coals  for  three  hours  at 
300  degrees,  and  then  extracted  with  caustic  potash.  By  treating 
the  extract  solution  with  cone,  acid  a bulky  flocqulent  precipitate 
of  a brownish  color.  The  yields  of  extract  were  found  to  increase 
when  the  coal  had  previously  been  oxidized.  Some  of  the  coals 
were  treated  with  nitric  acid  and  then  with  caustic  alkali,  a 
large  percentage  of  the  coal  was  extracted.  The  ultimate  analysis 


V 


. 


. 


. 


3. 


of  the  extract  showed  a decrease  in  carbon  and  hydrogen,  and  an 
increase  in  oxygen  and  nitrogen  over  that  of  the  original  coal. 

They  gave  the  analysis  of  the  extract  as  carbon  58-63.8,  hydrogen 
2.75-3.3,  oxygen  28-32.,  nitrogen  3. 3-4. 8 and  sulphur  .3-. 7 per- 
cent. They  concluded  that  the  coking  is  not  caused  by  nitrogen- 
ous constituents,  but  the  nitrogen  free  bodies  associated  with 
them;  and  the  ease  with  which  these  bodies  are  decomposed  or 
volatized  in  differednt  coal  governs  their  coking  properties. 

Donath  and  Margos ches  in  1502  4 added  powdered  permanganate 
to  their  alkali  solvent.  They  heated  till  there  was  no  further 
reduction,  reduced  the  excess  of  permanganate  with  sodium  formate 
and  filtered.  The  filtrate,  after  acidification,  was  treated  with 
a solution  of  calcium  chloride.  A precipitate  of  calcium  oxalate 
was  obtained.  Theare  experiments  show  that  lignites  and  bituminous 
coals  contain  a substance  or  substances  which  on  oxidation  give 
rise  to  acids  ( probably  humic  acids)  that  on  further  oxidation 
give  oxalic  acid. 

Boudouard  in  1919  5 found  that  coals  after  oxidation  in 
air  contained  acidic  products  which  were  soluble  in  alkali.  An 
experiment  was  made  on  seven  different  classes  of  coals.  The  coals 
were  first  oxidized  at  105  degrees,  then  treated  with  a 5 percent 
solution  of  caustic  potash,  the  soluble  portion  filtered  off  and 
precipitated  by  cone,  hydrochloric  acid;  this  precipitate  was 
washed  and  dried  at  110  degrees.  These  extracts  resembled  the 
humic  afcids  found  in  peat  and  had  the  formulae  C ^ H ]_4  0 g an(i 
Cl-  Hie  Cg  . It  was  noted  that  the  extraction  was  greatest  from 
the  lignite  and  bituminous  coals.  He  found  that  only  coals  appro- 
aching lignites  contained  these  acids  in  the  natural  state 


. 


• • 


* 


. 

■ 


. 

. . 


,«<j|  ' fl 

- 


4. 


( 1—5  percent),  but  they  could  be  detected  in  bituminous  coals 
after  oxidation  in  air  at  100  degrees  for  some  time.  He  also  ob- 
served that  the  invariable  effect  of  such  atmospheric  oxidation  is 
to  destroy  completely  the  coking  properties  of  a coal  and  to  di- 
minish the  carbon  content  and  increase  the  oxygen  and  hydrogen 
content  of  the  humic  acids.  He  concluded  that  the  substances  that 
were  oxidised  and  then  removed  ffom  coal  by  successive  treatment 
with  caustic  potash  were  of  celiulosic  nature. 

In  1912  6 Donath  and  Braunlich  made  a study  of  the  products 
obtained  by  repeated  fusions  of  the  coal  substance  with  alkaline 
hydroxide  (KOH)  at  250  degrees,  and  subsequent  extraction  with 
water.  Brown  coals,  charcoal,  and  carbonized  organic  matter  gave 
white  solutions.  Brown  coals  were  almost  completely  converted  into 
humic  acids  which  could  be  separated  into  two  fractions,  one  soluble 
in  cone,  alkali,  the  other  soluble  in  dilute  alkali. 

THEORETICAL 

Thiessen  and  White  7 studying  the  origin  of  coal,  concluded 
that  coal  is  a compounded  material,  which  can  be  divided  into  two 
large  classes,  one  celiulosic  in  nature,  a degredation  product  from 
pure  wood  or  plant  cellulose;  while  the  other  is  resinic  in  nature 
a degredation  product  of  the  gums,  waxes,  resins,  and  cellulose 
found  in  the  original  trees. 

Solvents  and  reagents  have  been  used  endeaving  to  separ- 
ate coal  into  these  two  groups,  the  celiulosic  from  the  resinic 
constituents  in  order  to  determine  separately  the  action  of  each 
during  carbonization. 

Lewes  in  hie  book  on  carbonization  conclude  : There 


. 


. 

. 

. 

. 


■ 

. 


. 

■ 


5 


are  two  kinds  of  resin  constituents,  one  easily  oxidizable,  soluble 
in  pyridene  and  saponifiable  by  alkalies,  and  which  on  weathering 
is  oxidized  into  humus  bodies  with  the  evolution  of  water  and  carbon 
dioxide;  the  other  class  non-oxidizable , not  saponified  by  alkalies 
rich  in  liquid  hydrocarbons,  but  not  rich  in  gas  upon  distillation. 

g 

Burgess  and  Wheeler  w contend  that  coal  contains  two 
different  types  of  bodies,  one  of  which  on  carbonization  gives  an 
excess  of  hydrogen  gases,  the  other  gives  an  excess  of  paraffin 
gases.  They  considered  the  cellulosic  constituents  as  the  hydrogen- 
yielding  bodies,  and  the  resinic  constituents  as  the  paraffin 
yielding  bodies.  They  claimed  tha  first  decomposition  product  of 
coal  to  be  resinous  nature  and  the  cellulosic  constituents  to  de- 
compose at  a much  higher  temperatures.  They  found  that  hydrogen 
predominated  beteen  $00-800  degrees,  and  that  methane  and  other 
paraffin  formed  from  60-80  percent  of  the  whole  gas  up  to  800  deg. 

Clark  and  Wheeler  10  with  the  use  of  pyridene  and 
chloroform  separated  the  cellulosic  from  the  resinic  constituents 
of  coal.  But  there  work  can  be  critized  because  of  the  gain  in 
percentage  of  nitrogen  and  oxygen  in  the  extract  and  residue  over 
that  of  the  original  coal.  The  nitrogen  indicated  that  pyridene 
was  a reagent  and  had  not  all  been  removed,  while  oxygen  indicated 
that  air  was  not  excluded. 

Porter  and  Taylor  ^ advance  the  following  hypothesis 
for  the  constitution  of  coal,  which  differs  fundamentally  from 
that  of  Burgess  and  Wheeler  in  supposing  that  the  cellulosic 
derivatives  decompose  more  easily  than  the  resinic  derivatives. 

The  less  altered  the  cellulosic  derivatives  decompose  more  easily 
then  the  resinic  derivatives.  The  cellulosic  derivatives  decompose 


. 


; 


- 


. 


- 

. 

. 


6 • 

so  as  to  yield  water,  carbon  dioxide,  and  carbon  monoxide,  and 
hydrocarbons.  The  resinic  derivatives  decompose  on  moderate 
heating  to  yield  paraffin  hydrocarbons,  with  hydrogen  as  a direct 
decomposition  product.  The  conclusions  of  Porter  and  Taylor 
are  better  based  then  those  of  Wheeler  and  Burgess.  It  is  more 
likely  that  the  hydrogen  evolved  bet?;een  700-900  deg.  is  product 
of  secondary  decomposition  of  a primary  decomposition  product. 

PURPOSE  OF  INVESTIGATION 

This  investigation  was  taken  up  with  the  following  ends 
in  view. 

1*  A study  of  the  conditions  best  adapted  for  the 
extraction  of  various  coals  with  aqueous  and  alcoholic  potash. 

2.  A study  of  the  properties  of  the  extract  and  residue 
obtained  by  this  extraction,  and  the  relation  of  each  to  the 
original  coal; 

(a)  By  means  of  ultimate  analysis. 

(b)  By  means  of  carbonization. 

3.  A comparison  of  the  percentage  extraction  obtained 
from  various  coals. 

4.  A comparison  of  the  extracts  and  residues  obtained 
from  the  various  coals. 


* 


‘ | 


. 

- 

. 

- 


7. 


EXPERIMENTAL 


Material. 

The  coals  used  in  this  work  were  from  different  local- 
ities and  of  different  types,  with  one  expection. 

The  five  coals  used  were  as  follows: 

1.  A non- coking  bituminous  coal  from  Utah. 

2.  A good  coking  coal  from  Franklin  County,  Illinois 
known  as  Makatan  Coal. 

3.  Another  good  coking  coal  from  Franklin  County, 
illinois,  known  as  Zeigler  Coal. 

4.  A good  coking  coal  from  Kentucky,  known  as  Jel- 
licc  Eastern  High  Volatile  Coal. 

5.  A good  coking  coal  from  Terra  Haute,  Indiana. 

With  the  exception  of  the  Zeigler  coal,  all  the  sample 

s had  been  air  dried.  All  five  coals  underwent  the  same  process 
for  preparation  of  the  samples.  The  coal  was  ground  in  a ball  mill 
until  all  passed  thru  a 100  mesh  sieve.  It  was  then  placed  in  air 
tight  jars,  until  used. 


Apparatus  and  Method. 

The  apparatus  that  was  necesaary  for  this  work  was 
very  simple.  An  electric  furnace  of  6 inch  diameter,  and  16  inch 
hight, wound  with  number  19  chromel  wire  furnished  the  heat  required. 

It  could  be  regulated  by  external  resistance  to  any  desired 
temperatures  between  75-550  deg. 

The  first  operation  was  to  extract  the  coal  with 
aqueous  or  alcoholic  potash.  This  was  done  by  placing  100  grams 
of  powdered  coal  with  500  cc.  of  10  percent  KOH  into  a 1000  cc. 


8 


Brlenmeyer  flask,  which  was  equipped  with  a reflux  condenser. 

This  was  placed  in  the  electric  furnace  and  heated  at  120  deg.  for 
48  hours. 

The  flask  was  then  removed  from  the  furnace,  and  the  contents 
filtered  while  hot  thru  a Buchner  funnel.  A dark  brown,  sometimes 
almost  black  liquid  filtered  thru,  leaving  the  residue  coal  on  the 
filter  paper.  This  coal  was  washed  with  water  until  all  the  extract 
was  removed.  This  coal  was  partly  dried  by  the  suction  thru  the 

funnel,  then  it  was  again  placed  in  the  Erlenmeyer  flask  with  a 
fresh  solution  of  aqueous  or  alcoholic  potash  and  then  refluxed 
again  for  48  hours.  On  all  the  samples  at  least  three  or  four 
extractions  were  necessary  to  remove  most  of  the  soluble  material. 

When  alcoholic  potash  \tfa3  used  the  extract  liquid  was  first 
placed  in  a 2000  cc.  distilling  flask,  and  the  pure  alcohol  distil- 
led off  and  recovered,  leaving  the  extract  in  a weak  alcoholic 
solution.  This  solution  was  treated  while  atill  hot  with  cone. 

HC1 , which  precipitated  the  extract  as  a brown  or  black  flocqulent 
precipitate,  rather  bulky,  and  also  volumes  of  carbon  dioxide 
were  evolved.  The  odor  of  these  acids  are  y^ery  sickening. 

This  precipitate  wa3  very  hard  to  handle,  and  was  of  colloid- 
al nature  when  precipitated  in  the  cold.  But  could  be  coagulated 
by  boiling  and  would  settle  on  standing.  But  even  this  bulky  mass 
was  hard  to  filter,  because  of  its  gelatine  like  nature,  it  required 
long  strong  suction  to  remove  the  liquid  from  the  precipitate. 

After  the  removal  of  the  mother  liquid  the  precipitate  was  washed 
for  long  periods  with  acid  water  to  remove  as  many  as  possible 
of  the  potassium  salts.  The  precipitate  was  removed  to  a drying 

bottle,  and  dried  at  110  deg.  in  an  atmosphere  of  nitrogen.  It  was 


- 


- 

. 

. 

. 

* 


- 


. 


9 


found  that  drying  the  precipitate  in  air  produced  oxidation  of  some 
of  the  substance,  which  could  readily  be  noticed  by  the  hairy  grow- 
ths which  appeared  over  the  sufface  of  the  substance.  The  precip- 
itate when  dried  was  powdered  and  weighed. 

The  residue  was  washed  with  HC1  acid  solution,  then  with 
alcohol,  and  finally  with  ether.  Then  it  was  dried  at  110  deg. 
in  an  atmosphere  of  nitrogen. 

The  output  of  the  yields  of  the  furnace  runs  was  found  to 
be  insufficient,  so  that  two  oil  bather  were  set  up  and  operated 
in  the  same  capacity  as  the  furnace. 

For  the  carbonization  of  the  residues  and  extract,  the 
furnace  was  used.  The  extract  or  residue  was  placed  in  a 100  cc. 
distillation  flask,  equipped  with  a thermometer  and  connected  to 
a source  of  nitrogen,  the  side  arm  of  the  flask  was  connected  to 
a bottle,  used  a3  a trap  for  the  water  of  decomposition,  and  the 
tars;  connected  to  the  first  bottle  was  a similar  bottle  contain- 
ing a solution  of  sulphuric  acid  and  cadmium  nitrate,  which  removed 
the  ammonia  and  the  sulphur  from  the  gases,  which  were  led  from 
here  into  an  aspirator  bottle  where  they  were  collected  and  measur- 
ed over  salt.  The  apparatus  va.3  flushed  out  with  nitrogen  before, 
and  after  the  carbonization  run.  The  furnace  was  allowed  to  heat 
to  400  deg.  and  kept  at  that  temperature  until  all  the  gases  were 
evolved  from  the  sample.  The  tar  and  water  were  weighed,  and  the 
gases  collected  over  salt  water  were  analized  by  means  of  a modified 
Orsat  Apparatus. 

An  ultimate  analysis  of  each  orignial  coal,  extract  and  re- 
sidue was  made,  The  usual  methods  were  employed. 

Carbon  was  determined  by  the  Parr  Total  Carbon  Apparatus. 


. 


. 


. 


. 


. 


. 

. 


. 


. 


; <!  I 


. 


10, 

The  B.  t.  u.  was  determined  by  the  Parr  Oxygen  Bomb. 

The  sulphur  was  determined  by  fusion  in  a Peroxide  Bomb,and  pre- 
cipitated and  weighed  as  Barium  sulphate. 

The  nitrogen  and  oxygen  were  calculated  by  means  of  the  Dulong 
Formula. 


11. 


DISCUSSION. 

The  first  extractions  were  made  on  the  Makatan  and  Utah 
coals  with  a 10  percent  solution  of  aqueous  caustic  potash.  The 
extractions  were  very  poor  and  of  to  high  an  ash  content  to  be  of 
any  analytical  value.  The  extracts  were  a grayish  color  and 
contained  only  a small  amount  of  volatile  material.  This  indicated 
that  the  coal  had  only  slighly  oxidized  or  the  quantity  of  extract 
would  have  been  increase  by  humic  acid3. 

Table  I 


Coal 

Run  No 

Extractions 

Perce: 

Illinois,  Makatan 

1 

three 

1.0 

n n 

2 

three 

5.2 

Utah 

3 

two 

2.6 

« 

4 

three 

3.5 

n 

5 

three 

4.6 

The  extracts  were  non-coking.  Since  the  action  of  aqueous 
potash  on  these  non-oxidized  coals  proved  to  be  very  poor  in 
extracting  organic  matter,  alcoholic  potash  was  decided  upon  to 
take  its  place,  and  the  result  proved  more  successful. 

The  coal  was  treated  with  alcoholic  potash  in  the  same 
manner  it  had  been  treated  with  aqueous  potash  solution. 

The  first  change  was  that  the  alcohol  wet  the  coal 
immediately,  while  the  water  failed  to  do  this.  The  resinic  con- 
stituents are  also  more  soluble  in  alcohol  than  in  water,  fhich 
increased  greatly  the  saponifying  power  of  the  KOH,  becuase  they 
were  in  a better  condition  to  be  attack  by  it.  The  yields  were 


. 


* 


. 

- 

- 

. 

. 

. 


. 

. 


. 


12. 

larger  than  before  and  of  a high  percentage  of  organic  matter. 


The  total 

yields  are 

given  in 

Table 

II  . 

Table 

II 

Coal 

Run  No. 

Extraction 

Percent  Extract. 

Jellico, 

E.  H.  V. 

1 

four 

6.3 

n 

n 

2 

two 

3.0 

Zeigler, 

Illinois . 

3 

one 

4.4 

n 

t! 

4 

three 

6.0 

Indi ana 

5 

four 

12.8 

« 

6 

three 

11.0 

Makatan 

7 

two 

6.0 

The  extracts  of  the  first  three  coals  listed  above  were 
dark  brown  in  color,  varying  in  shade,  but  the  extract  from  the 
Makatan  coal  was  black  like  the  coal  itself. 

Before  discussing  the  properties  of  the  extract  and  residue 
obtained,  a clearer  conception  of  these  two  substances  may  be 
obtained  from  the  work  of  Lewes. 

In  his  theory  he  explains  that  "humus"  and  "resin"  body 
does  not  mean  a definate  compound,  but  merely  bodies  of  this  char- 
acter — resin  bodies  all  contain  above  5 percent  hydrogen,  while 
the  humus  bodies  all  contain  hydrogen  from  5 percent  downwards. 

In  concluding  the  discussion  of  the  ultimate  analysis  of  humus 

and  resin  acid  substances  he  gave  this  formula. 

Carbon  Hydrogen  Oxygen 
Humus  Acid  63  5 32 

Resinic  75  11  10 

Refering  first  to  the  analysis  of  the  Jellicao.  E.  H.  V. 

Coal  and  Table  Ho  III,  the  results  show  in  the  case  of  the  extract 
an  increase  in  hydrogen  and  a decrease  in  oxygen  and  carbon  content 
and  the  ratio  of  these  indicate  that  it  is  a resinic  compound. 

The  residue  showed  an  decrease  in  carbon  and  hydrogen  and  an  in- 
crease in  oxygen.  The  ratio  of  these  Elements  indicate  that 


13 


the  cellulosic  constituents  predominate.  In  considering  that  the 
analysis  errors  ate  due  to  the  fact  that  all  of  the  moisture  and 
ash  ( due  to  potassium  salts)  waa  not  removed  from  the  extract  and 
residue.  It  was  then  necessary  to  convert  each  to  the  Moisture- 
Ash  free  bases  for  comparison,  and  this  factor  might  cause  an 
error  in  results. 

The  analysis  of  gases  ( Table  VII)  from  the  carbonization 
of  the  residue  indicated  high  yields  of  paraffins  as  well  as 
carbon  monoxide,  carbon  dioxide  and  hydrogen.  It  is  probable 
that  not  all  of  the  resinic  constituents  were  extracted,  because 
they  were  not  saponifiable.  For  the  high  yield  of  paraffins  was 
probably  due  to  there  decomposition. 

Refering  to  the  analysis  of  Makatan  Coal,  (Table  IV  ) it 
is  noticed  that  not  a great  deal  of  difference  between  that  of 
the  original  coal,  the  extract  and  the  residue.  In  explaining 
why  this  coal  analysis,  first  it  might  be  due  to  the  fact  that 
a 30  percent  solution  of  sodium  hydroxide  was  used;  second,  that 
some  of  the  coal  was  oxidized  to  humic  acid.  Yet  the  extract  form 
ed  a coke,  and  the  residue  did'nt  coke.  This  shows  that  most  of 
the  resinic  material  was  extracted.  The  carbonization  data 
( Table  VII  ) however  differed  little  from  the  residue  of  the 
other  coals,  showing  that  cellulosic  material  predominated  in  the 
residue . 

The  analysis  of  the  Zeigler  Coal,  extract,  and  residue 
are  given  in  Table  V,  It  ia  immediately  noticed  that  there  is 
a considerable  loss  in  the  carbon  cantent  and  a gain  in  the  oxy- 
gen content  in  the  products  against  the  original  coal.  This 

might  be  accounted  for  by  the  fact  that  the  coal  was  fresh  when 


• 

■ 


14. 

the  moisture,  and  approximate  analysis  was  run,  but  was  allowed  to 
stand  before  the  ultimate  analysis  was  made.  There  was  also  an 
oxidation  of  the  residue  and  extract,  evidently  the  air  was  not 
excluded. 

The  ratio  of  the  hydrogen,  carbon  and  oxygen  in  the  extract 
indicate  that  it  is  of  resinic  nature.  The  hydrogen  content  in 
the  residue  is  a little  high  to  conform  to  the  analysis  of  the 
cellulosic  constituents.  The  analysis  of  the  gases  from  the  carbon- 
ization of  the  residue  differ  very  little  from  those  of  the  Jellico 
Coal,  The  extract  gave  a good  coke,  while  the  residue  did  not. coke. 

The , ultimate  analysis  of  the  Indiana  Coal,  extract  and  re- 
sidue are  given  in  Table  V,  It  is  noticed  that  there  is  a loss  in 
hydrogen  and  a gain  in  oxygen  on  the  balancing  of  the  products 
against  the  original  coal.  This  gain  of  oxygen  in  the  extract 
and  residue  show  oxidation,  and  that  air  had  not  been  excluded  all 
of  the  time.  It  is  not  probable  that  the  extract  absorbed  much 

oxygen  because  it  had  practically  no  unsaturation,  but  the  residue 
was  highly  unsaturated,  much  more  so  than  the  original  coal.  Yet 
the  extract  showed  a gain  in  hydrogen  and  a loss  in  carbon  similar 
to  the  other  coals.  This  residue  conformed  with  those  of  the 
other  coals,  showing  an  increase  in  carbon  and  oxygen  and  a de- 
crease in  hydrogen  comparing  to  the  original  coal. 

The  extract  and  residue  of  the  Indiana  coal  were  both 
carbonized,  since  there  was  enough  of  the  extract  left  after  anal- 
ysis for  a sample.  In  comparing  the  gas  analysis  ( Table  VII  ) 
of  these  two,  it  is  noticed  that  the  extract  contained  only  one- 
half  as  much  carbon  dioxide,  and  only  one-half  as  much  hydrogen 
a3  the  residue,  but  contained  three  times  as  much  paraffin 


- 


■ 


. 

* 


T 


' 


, 


. 


15 


hydrocarbons.  This  is  consistent  with  the  result  previously  obtain- 
ed. That  is  the  residue  contains  the  cellulosic  constituents, 
which  decompose  to  give  carbon  dioxide,  hydrogen  and  water,  while 
the  resinic  constituents  in  the  extract  on  decomposition  give  an 
excess  of  paraffin  hydrocarbons.  A fragil  coke  was  obtained  from 
the  extract,  while  the  residue  failed  to  coke. 


- 

, 


16 


SUMMARY. 

The  conclusions  drawn  from  this  investigation  are: 

1.  That  only  a negligibly  small  amount  of  organic 
substances  can  be  removed  from  non-oxidized  bituminous  coals  by 
treatment  with  aqueous  caustic  potash. 

2.  That  alcoholic  caustic  potash  will  remove  from 
non-oxidized  bituminous  coals  a considerable  quantity  of  organic 
substances. 

3.  That  this  extracted  organic  substance  consists 
mainly  of  resinic  constituents,  while  the  residue  is  composed  in 
general  of  cellulosic  constituents. 

4.  That  the  extract  contained  the  coking  and  binding 
constituents  of  the  original  coal,  and  that  the  residue  left  after 
extraction  could  not  be  coked. 


IJ 


■ 


. 


. 


17 


BIBLIOGRAPHY. 

I.  J.  See.  Chem  Industry  27  , 149,  (1908) 

3.  Chem  Soc.  A.  48  , 876  (1885) 

3.  J.  of  Soc.  Chem  Industry  17  , 1013  (l£S8) 

4.  Chem  Industrie  , 226,  (1902) 

5.  Bull,  of  Soc.  Chimi q._5  ,365,  (1909) 

6.  Chem  Zeit.  36  , 373,  (1912) 

7.  U.  S.  Survey  Bull.  No  383  & Bull.  B.  of  Mines  No  36. 

8.  Lewes,  Carbonization  of  Coal. 

S.  J.  0.  C.  Vcl  103  , 1705  (1913) 

10.  J.  C.  C.  Vol  107  , 1318  (1915) 

II.  Tech,  paper.  B.  cf  Mines.  No  140 


. 


18. 

Table  III. 

Ultimate 

Analysis  of  Jellico, 

E.  H.  V.  Coal,  Kentucky. 

Original 

Total  Percent  Coal 

As  Rec 

* d M-A  Fre  e 

of 

or 

Moisture 

1.66 

Percaat  Coal 

Extract  & Residue. 

Ash 

2.60 

Carbon 

81.00 

84.60 

63.42 

Hydrogen 

4.95 

5.17 

4.68 

Oxygen 

7.44 

7.77 

9.54 

Nitrogen 

1.65 

1.73 

1.62 

Sulphur 

.70 

.73 

.74 

B.  t.  u. 

14,300 

14,950 

14,465 

After  extraction  of  coal  with  alcoholic  XOH. 

Extract 

Residue 

As  Rec* 

d M-A  Free  Percent 

As  Rec'd  M-A  Free  Percent 

Coal 

Coal 

Moisture 

5.91 

6.15 

Ash 

33.93 

3.65 

Carbon 

53.80 

76.67  3.38 

75.50  83.70  80.04 

Hydrogen 

10.06 

14.34  .54 

3.81  4.33  4.04 

Oxygen 

4.73 

6.74  .39 

8,75  9.70  9.25 

Nitrogen 

.50 

.71  .03 

1.50  1.66  1.59 

Sulphur 

1.08 

1.54  .06 

.64  .71  .66 

B.  t.  u. 

13,735 

19,600  865 

12,745  14,150  13,600 

Yield 

6.3 

4.4 

19 


Table  IV, 

Ultimate  Analysis  of  Makatan  Coal,  Franklin  Co.,  Illinois. 


Original  Total  Percent  Coal 

As  Rec’d  M-A  Free  of 

or  Extract  & Residue. 


Moisture 

2.08 

Percent  Coal 

Ash 

7.15 

Carbon 

75.60 

63.30 

82.80 

Hydrogen 

4.31 

4.75 

4.69 

Oxygen 

8.23 

9.05 

10.01 

Nitrogen 

1.40 

1.54 

1.24 

Sulphur 

1.23 

1.36 

1.40 

B.  t.  u. 

13,080 

14,400 

14,075 

After  extraction  of  the  coal  with 

alcoholic  KOH 

. 

Extract 

Residue 

Moisture 

As  Rec'd 
5.72 

M-A  Free  Percent 
Coal 

As  fcec 
2.68 

* d M-A  Free 

Percent 

Coal 

Ash 

15.00 

11.41 

Carbon 

65.60 

62.70  3.93 

71.00 

82.74 

78.87 

Hydrogen 

3.27 

4.12  .31 

4.03 

4.70 

4.46 

Oxygen 

8.05 

10.21  .49 

8.63 

10.00 

9.53 

Nitrogen 

.50 

.63  .06 

.08 

1.20 

1.14 

Sulphur 

1.66 

2.34  .11 

1.17 

1.36 

1.29 

B.  t.  u. 

11,040 

14,270  685 

12,080 

14,050 

13,396 

Yield 

6,00 

4.80 

95.20 

20 


Table  V. 

Ultimate  Analysis  of  Zeigler  Coal,  Franklin  County,  Illinois. 


Moisture 

As  Rec’ 
7.07 

Original 

d M-A  Free 
or 

Percent 

Coal 

Total  Percent  Coal 
of 

Extract  & Residue. 

Ash 

10.05 

Carbon 

66.00 

79.61 

76.23 

Hydrogen 

4.36 

5.26 

5.26 

Oxygen 

10.17 

12.29 

16.58 

Nitrogen 

1.30 

1.57 

1.19 

Sulphur 

1*05 

1.27 

.65 

B.  t.  u. 

11,565 

13,950 

13,010 

After  extraction  of 

the  coal 

with  alcoholic  KOH. 

Extract 

Residue . 

Moisture 

As  Rec 
4.56 

'd  M-A  Free 

Percent 

Coal 

As  Rec'd  M-A  Free 

2.80 

Percent 

Coal. 

Ash 

6.00 

6.45 

Carbon 

72.30 

80.2q 

5.83 

66.60  75.60 

70.40 

Hydrogen 

5.87 

6.57 

.47 

4.76  5.25 

4.80 

Oxygen 

9.94 

11.06 

.78 

15.37  17.04 

15.80 

Nitrogen 

.80 

.88 

.08 

1.32  1.45 

1.18 

Sulphur 

.53 

.59 

.04 

.60  .66 

.62 

B.  t.  u. 

13,300 

14,680 

1,060 

11,680  12,880 

11,950 

e.oo 


Yield 


7.2 


Table  VI 


31 


Ultimate  Analysis  of  Coal  from  Terra  Haute,  Indiana. 

Original  Total  Percent  Coal 

of 


Moisture 

As  Rec'd 
1.73 

M-A  Fre  e 
or 

Percent  Coal 

Extract  & Residue 

Ash 

S.10 

Carbon 

71.00 

79.70 

73.18 

Hydrogen 

4.68 

5.47 

4.00 

Oxygen 

8.13 

9.13 

11.24 

Nitrogen 

1.40 

1.57 

1.52 

Sulphur 

3.78 

4.24 

4.06 

B t . u. 

13,900 

14,300 

13,360 

After  extraction  of  the  coal 

with  alcoholic  KOH. 

Extract 

Residue 

Moisture 

As  Rec'd 
2.3o 

A-M  Free  Percent 
Coal 

As  Rec 
4.20 

1 d A-M  Free 

Percent 

Coal 

Ash 

4.50 

25.00 

Carbon 

67.00 

71.60  , 7.18 

56.60 

80.00 

72.00 

Hydrogen 

6.04 

6.47  .65 

2.63 

3.73 

3.35 

Oxygen 

16.96 

16.18  l.ei 

7.47 

10.50 

9.43 

Nitrogen 

1.10 

1-18  .12 

1.10 

1.55 

1.40 

Sulphur 

3.20 

3.37  .24 

3.00 

4.33 

3.82 

B » t . u * 

12,285 

13,100  1 ,310 

9,440 

13,300 

12,050 

Yield. 

11.8 

10 

90 

22 


Table  VII 

Carbonization  Tests. 

After  extraction  of  the  coal  with  alooholic  KOH. 

Residue.  Extract. 


Zeigler . 

Makatan.  Indiana. 

E.  H.  V. 

Indiana. 

Sample 

50  gm. 

50 

gm.  5o  gm. 

50  gm. 

lOgm . 

Final  Temp. 

400 

400 

370 

400 

370 

Tar  & Water 

6.9  gm . 

9.0 

gm . 9,0  gm 

6.6  Gm . 

2.2  gm. 

ReBidue 

41  " 

35 

« 38  M 

38  " 

Appearance  of 
residue 

Powder  Powder 

Powder 

Powder 

P owde  r 

App.  of  HoS  at 

270  Deg 

. 250 

deg. 28 o deg. 

150  deg. 

150  deg 

Vol  of  Gas , 

2700  cc. 

2700 

cc.  2000  cc. 

2700  cc. 

360  cc . 

Analysis  of  gases  on  the  Nitrogen  Free  Basis. 


Carbon  Dioxide 

21.2 

30.1 

50.9 

24.0 

26.^ 

Oxygen 

6 . 6 

0 

.1 

.7 

4.g 

Unsat. 

2.9 

2.1 

2.6 

3.6 

4-1 

Benzene 

0. 

.6 

.5 

1.5 

.2 

Hydrogen 

lo.50 

39.3 

39.8 

9.9 

14.7 

Carbon  Monoxide 

12.4 

4.7 

3.4 

7.1 

3.3 

Ethane 

33.5 

7.3 

6.3 

0.0 

-3.6 

Methane 

13.0 

16.0 

Coking 

6.2 

Tests  at  930 

49.0 

35.6 

Residues  from  each  coal  remained  a powder. 

Extracts  from  each  coal  gave  a good  but  fragil  coke. 




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